The present invention relates to the novel compounds 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol and processes for preparing the aforementioned butanols and acetates thereof.
There has been considerable work performed relating to substances which can be used to impart (or enhance) flavors to (or in) various consumable materials. These substances are used to diminish natural materials some of which may be in short supply and provide more uniform properties in finished products. Violet, green, floral, woody and piney aroma notes are particularly desirable for many uses in fruit flavoring compositions and consumable articles, e.g., foodstuffs. Leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone and musky aromas are particularly desirable in perfume compositions.
The flavor and fragrance material having the structure: ##STR1## is disclosed in British Patent No. 1,305,621 issued on Feb. 7, 1973.
4-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-1-YL)-2-BUTANONE HAVING THE STRUCTURE: ##STR2## may be synthesized according to the technique of Wolf and Zink, Volume 56, Helvetica Chimica Acta., Fasc 3 (1973) pp. 1062-1066, or according to Examples I and II of Rowland, U.S. Pat. No. 3,436,421 issued on Apr. 1, 1969 by means of bromination of -dihydroionone followed by debromination. 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone having the structure: ##STR3## is also produced in this process as a bi-product thereof (B.P. 65.degree. C at 0.15 mm Hg. pressure). 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone is also shown to be a bi-product in the cyclization of ionone to beta ionone by Kruk and De Boer in Volume 87 Recueil (1968) pp. 641-654 as an intermediate in preparing other perfumery compounds. The compound having the structure: ##STR4## is disclosed in Japanese Patent No. 7121,015 (Sakan and Isoe)issued June 14, 1971.
Japanese Patent No. 7404,391 discloses a synthesis of the compound having the structure: ##STR5## from a compound having the structure: ##STR6## This patent indicates that the synthesized compound can improve the aroma and quality of distilled spirits. Compounds of the structures: ##STR7## are indicated to be intermediates in the synthesis gamma-dihydroionone by Stoll, Helv. Chim. Acta., 38, 1587 (1955) and British Patent No. 794,416. The synthesis of the compound having the structure: ##STR8## is disclosed by Naves and Bachmann, Helv. Chim. Acta., 26, 2151 (1943).
Sato and Mashima, Tetrahedron Letters No. 22, Page 1803 (1969) discloses the synthesis of theaspirone from the material having the structure: ##STR9## but no odor qualities of this acetate are set forth therein. Demole et al., Helv. Chim. Acta., 53, 541 (1970) discloses the synthesis of the alcohol having the structure: ##STR10##
Arctander, "Perfume and Flavor Chemicals" (Aroma Chemicals), 1969 discloses in Vol. I at 1775 "beta-ionol" having the structure: ##STR11## as having a "sweet, oily-herbaceous, warm odor with floral-balsamic undertones . . . some resemblance to Labdanum notes" Arctander further states that "this secondary alcohol has been suggested for use in perfume compositions as a modifier in various types of floral and non-floral fragrances. It blends well with Labdanum, Lavender, Lavandin, Clary Sage, etc. and it has a refreshing effect upon Rose types. It performs pleasantly with the eliphatic aldehydes into refreshing notes varying from Pine to Rose, and it was at one time used in several types of detergent fragrances". It is produced by reduction of beta-ionone with sodium alcoholate or by Meerwein-Ponndorf-Verley reduction.